Preparations of polycarbynes

ABSTRACT

Polycarbynes prepared from a soluble source of electrons and an organic monomer or co-monomer containing at least one carbyne group in an ethereal, polyethereal, or hydrocarbon solvent are presented. A wide variety of arylcarbyne and/or alkylcarbyne monomers and co-monomers can be combined with a source of electrons soluble in an ethereal, polyethereal, or hydrocarbon solvent to form novel polycarbyne polymers. These polycarbyne polymers can be used to form synthetic diamond materials, fibers, and other materials that can withstand extreme conditions.

The present invention was made with Government support under Grant No.GM 35153 awarded by the National Institute of Health. The Government hascertain rights in the invention.

FIELD OF THE INVENTION

The present invention relates to polycarbynes. More specifically, thepresent invention relates to methods for preparing polycarbynes bycombining a source of soluble electrons and a carbyne-containingmonomer. The present invention also relates to compositions ofpolycarbynes.

BACKGROUND OF THE INVENTION

Polycarbynes are polymers that can be used for the preparation ofdiamond-like carbon films and in applications that require materials towithstand extreme conditions. Extreme conditions are conditions in whichmany materials typically fail or lose their structural integrity. Someexamples of extreme conditions include extreme temperatures andpressures, high shear or tensile forces, and/or corrosive environments.Presently, metals, high performance plastics, diamonds and other highstrength materials are used in many applications in which the materialsare exposed to extreme conditions. However, these materials can becumbersome, expensive and difficult to work with.

For example, diamond is used in and has been proposed for manyapplications in which materials that can withstand extreme conditionsare needed. Diamond is a material from which cutting and drilling toolscan be made. Diamond has been proposed for many electronic applications,such as the material from which microelectronic chips are made, becauseit has high mobility, a high breakdown strength, and a high radiationhardness. However, acquiring natural diamond can be very expensiveand/or time consuming because of its scarcity and the difficulty withwhich it is mined. The difficulty of acquiring natural diamond has ledto the need for development of synthetic diamond materials.

Presently, there are several methods for preparing synthetic diamondmaterials. These methods include use of heat and pressure, chemicalvapor deposition, and ultrasonically generated emulsions. Every yeartons of commercially manufactured diamond materials are made by heatinggraphite to about 1370° C. while subjecting it to about 50,000atmospheres of pressure. This heat and pressure technique convertsgraphite's layered sheet-like atomic structure to diamond'sthree-dimensional tetrahedral crystalline network. This technique,however, is cumbersome and requires large and expensive machinery.

Chemical vapor deposition is a cheaper means of manufacturing syntheticdiamond. In this process, carbon-containing gas gets decomposed, withmicrowaves or some other energy source, and the liberated carbon settleson a surface, such as glass or silicon. As the carbon settles, a thinfilm of solid diamond or diamond-like material develops. However, thisfilm-forming process has not seen wide commercial success because it isvery slow and difficult to control.

A recently developed method for preparing diamond-like materials wasreported by Glenn T. Visscher et al. in Science, 260, 1496-1498 (1993).This method for preparing diamond-like materials involves transforming aliquid precursor into a synthetic diamond film. In order to achieve thetransformation, α,α,α-trichlorotoluene is reduced in tetrahydrofuran,using an ultrasonically generated emulsion of a sodium-potassium alloy,to form poly(phenylcarbyne). The poly(phenylcarbyne) is then pyrolizedto form a synthetic diamond material. This process is complex andrequires a highly explosive alloy to form the intermediatepoly(phenylcarbyne).

Using metal compounds to polymerize organohalides is not new in the art.U.S. Pat. No. 5,211,889 issued on May 18, 1993 to Reuben D. Rieke,specifically discloses examples of soluble highly reactive calciumreacting with dihalothiophenes and dihalobenzenes, for example, to formpolymeric materials. However, there is no indication thatcarbyne-containing organohalides, such as α,α,α-trichlorotoluene, canform polycarbynes using the highly reactive calcium.

A need exists for a facile, relatively safe and inexpensive method ofproducing polycarbynes with reasonably high yields. This facile methodshould be readily adaptable to the production of a variety ofpolycarbyne materials. Once produced, polycarbynes can be converted intoa synthetic diamond material, a plastic material, or other high strengthmaterial that maintains its structure in extreme conditions.

SUMMARY OF THE INVENTION

The present invention relates to the composition and preparation ofpolycarbynes. A method for preparation of a polycarbyne includescontacting a soluble source of electrons with an organic monomer orco-monomer in an ethereal, polyethereal, or hydrocarbon solvent. Theorganic monomer or co-monomer contains at least one carbyne group, andthe soluble source of electrons is soluble in an ethereal, polyethereal,or hydrocarbon solvent. The term "organic" refers tohydrocarbon-containing groups wherein the majority of atoms are carbonand hydrogen. This includes within its scope alkyl groups, aryl groups,and arylalkyl groups. It is understood that inorganic atoms and/orgroups, such as silicon, nitrogen, phosphorous, oxygen, and sulfur, canbe included within the organic monomers. Such groups or atoms can bepresent as long as they do not interfere with or participate inpolymerization.

The soluble source of electrons can be a highly reactive metal species,which is made by contacting in an ethereal, polyethereal, or hydrocarbonsolvent, a metal salt, soluble in an ethereal, polyethereal, orhydrocarbon solvent, with a solubilized reducing agent having areduction potential of -1.5 volts or more negative relative to thestandard calomel electrode (SCE). This highly reactive metal species canthen be combined with an organic monomer or co-monomer containing atleast one carbyne group to form a polycarbyne. When the organic monomeror co-monomer contains at least one carbyne group that is bonded to analkyl group a poly(alkylcarbyne) is formed. When the organic monomer orco-monomer contains at least one carbyne group that is bonded to an arylgroup, a poly(arylcarbyne) is formed. When the organic monomer orco-monomer contains at least one carbyne group that is bonded to anarylalkyl group, a poly(arylalkylcarbyne) is formed.

Most of these polycarbynes are novel polymers. Their compositions varywith the types of alkyl, aryl or arylalkyl carbyne-containing monomersand/or co-monomers polymerized to form these polymers. These polymerscan be used to make synthetic diamond materials, polymer fibers andother materials that can withstand extreme conditions.

As used herein, the term "polycarbyne" or "polycarbyne compound" refersto polymers or oligomers containing "alkylcarbyne," "arylcarbyne" or"arylalkylcarbyne" moieties or mixtures thereof. As used herein, thephrase "alkyl" refers to a saturated linear, branched, or cyclichydrocarbon group, and the phrase "aryl" refers to a mono-, di- orpolynuclear aromatic hydrocarbon group. As used herein, the phrase"arylalkyl," or alternatively "alkylaryl," refers to a group containingboth aryl and alkyl moieties. The phrase "carbyne" refers to a grouphaving a carbon atom bonded to three leaving groups prior topolymerization. These leaving groups included in the carbyne group arereplaced during polymerization either directly or indirectly by anothercarbyne carbon.

The phrase "arylcarbyne," as used in the nomenclature of the polymers,monomers, and co-monomers discussed herein, refers to moietiescontaining one or more carbyne groups bonded to an aryl group. Forexample, an arylbiscarbyne is an arylcarbyne that contains two carbynegroups attached to an aryl group. A polymer formed from anarylbiscarbyne monomer is a poly(aryldicarbyne). The phrase "bis" isused to describe a monomer that contains two carbyne groups, and the"phrase" di is used to describe a polymer resulting from thepolymerization of a bis monomer. The phrase "alkylcarbyne," as used inthe nomenclature of the polymers, monomers, and co-monomers discussedherein, refers to moieties containing one or more carbyne groups bondedto an alkyl group. For branched or long chain alkyl groups, the carbyneis bonded to a terminal carbon, e.g. of a methylene group. For example,an alkylbiscarbyne is an alkylcarbyne that contains two carbyne groupsattached to an alkyl group. A polymer formed from an alkylbiscarbynemonomer is a poly(alkyldicarbyne). The phrase "arylalkylcarbyne," oralternatively, "alkylarylcarbyne", as used in the nomenclature of thepolymers, monomers, and co-monomers, discussed herein, refers tomoieties containing one or more carbyne groups bonded to an arylalkyl oran alkylaryl. The phrase "arylcarbyne-alkylcarbyne" or"alkylcarbyne-arylcarbyne" as used in the nomenclature of the polymers,monomers, and co-monomers discussed herein, refers to moietiescontaining one or more carbyne groups bonded to an aryl group and one ormore carbyne groups bonded to an alkyl group. The term "polymer" or"polymeric" is used herein in its most general sense to mean a compoundconsisting of repeating structural units. The term "monomer" or"monomeric" is used herein in its most general sense to mean a compoundconsisting of singular structural units. The term "co-monomer" is usedherein in its most general sense to mean a compound consisting of morethan one molecular type of singular structural units. An organic monomeror co-monomer can contain one or more aryl groups, one or more alkylgroups, and/or one or more arylalkyl groups.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents a graph of: (a) UV-vis electronic spectrum(cyclohexane) and (b) fluorescence spectrum (cyclohexane, excitationwavelength=300 nm) of poly(phenylcarbyne) obtained in accord with thepresent invention.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

The present invention is based upon the discovery that a soluble sourceof electrons can be combined in an ethereal, polyethereal, orhydrocarbon solvent with organic monomers or co-monomers to formpolycarbyne polymers. By combining the soluble source of electrons witha variety of arylcarbyne monomers or co-monomers, alkylcarbyne monomersor co-monomers, or arylcarbyne-alkylcarbyne co-monomers,arylcarbyne-arylalkylcarbyne co-monomers, alkylcarbynearyl-alkylcarbyneco-monomers, arylalkylcarbyne monomers or co-monomers, for example, newpolymers can be formed.

Soluble Source of Electrons

Any source of electrons, soluble in an ethereal, polyethereal, orhydrocarbon solvent, having a reduction potential of -0.2 or morenegative, relative to the standard calomel electrode (SCE), can be usedto form a polycarbyne from the organic monomers or co-monomers pursuantto the present invention. In accord with the present invention, thesoluble source of electrons should be sufficiently soluble in anethereal, polyethereal or hydrocarbon solvent to react with the monomeror co-monomer in solution. By this it is meant that the reaction withthe monomer or co-monomer does not occur on the surface of a solidparticle. Preferably, "soluble" refers to a compound that is at least0.5 wt-% soluble in an ethereal, polyethereal, or hydrocarbon solvent,and more preferably, at least 1 wt-% soluble.

Ethereal, polyethereal, or hydrocarbon solvents in which the source ofelectrons should be soluble include, but are not limited to: ethylether, tetrahydrofuran, glyme, diglyme, triglyme, benzene, hexane andthe like. If a hydrocarbon solvent is used, it preferably contains asecondary solubilizing agent such asN,N,N',N'-tetramethylethylenediamine (TMEDA), or other diamine orbidentate ligand capable of solubilizing the starting materials andproduct.

A variety of electron transfer compounds, e.g., macrocyclic, polyethers,cryptates, polyenes, and the like, in combination with alkali metals areusable sources of soluble electrons that are capable of interacting withorganic monomers or co-monomers to form polycarbynes. Preferably, thesoluble source of electrons contains a polyene. More preferably, thesoluble source of electrons contains an aromatic polyene, i.e., an areneor polyarylene, such as an aromatic electron-transfer compound. Examplesof aromatic electron-transfer compounds include, but are not limited to,biphenyl, naphthalene, and anthracene. Compounds such as these aretypically capable of transferring electrons in an oxidation reductionreaction through the formation of radical anions. Specific examples ofsuitable solubilized sources of electrons include: alkali metal salts ofaromatic anions, such salts being, for instance, sodium naphthalenide,lithium naphthalenide, sodium anthracenide, lithium anthracenide, sodiumbiphenylide or lithium biphenylide; alkali metal-polyether solvates;alkali metal-crown ether solvates; alkali metal-cryptate solvates, etc.Preferably, the soluble source of electrons is an alkali metal arenesalt. More preferably, the soluble source of electrons is a combinationof an alkali metal cation and an anion of an aromatic electron transfercompound, such as biphenyl, anthracene, or naphthalene. Most preferablythe soluble electron source is performed. Of the preformed alkali metalarene salts, the most preferred is lithium biphenylide.

By "preformed" it is meant that the alkali metal and about 1-1.2 molarequivalents of the arene are allowed to react substantially completely,i.e., until substantially all the alkali metal is consumed, beforecontacting any monomer in accord with the present invention. Theformation of the preformed reducing agent typically takes place in anethereal, polyethereal, or hydrocarbon solvent, and generally issubstantially complete in about two hours.

A variety of alkali metals can be in combination with the macrocyclicpolyethers, cryptates, polyenes and the like to form a soluble source ofelectrons usable in the present invention. Some examples of usablealkali metals in the present invention are: lithium, sodium, potassium,rubidium, cesium and/or mixtures thereof.

Although, use of an alkali metal arene salt as the soluble source ofelectrons is preferred, a soluble highly reactive metal species can alsobe prepared and used as a soluble source of electrons in accord with thepresent invention. In general, the previously discussed sources ofsoluble electrons, such as an alkali metal arene salt, can be used toreduce soluble metal salts, such as a calcium(II) salt, a barium(II)salt, a strontium(II) salt, a copper I or II salt or mixtures thereof,to form soluble highly reactive metals that are suitable sources ofsoluble electrons to form polycarbynes. As used herein, the term "highlyreactive" refers to the reactivity of a metal species, such as calcium,strontium, barium, copper, or mixtures thereof in organic reactions,particularly oxidative addition reactions. As used herein, a metalspecies is highly reactive if it reacts with a wide variety of primary,secondary, and particularly tertiary alkyl halides in relatively highyields, for example in greater than about 50% yields, preferably ingreater than about 70% yields.

These soluble highly reactive metal species are composed of formallyzerovalent metal atoms in combination or in complexation with asolubilizing agent. Preferably, the highly reactive metal speciescontains formally zerovalent non-alkali metal atoms. By "formallyzerovalent" it is meant that the formal oxidation state, or charge, isequal to the group number (i.e., 2 for calcium) minus the number ofunshared electrons (i.e., 2 for calcium) minus the number of bonds(i.e., 0 for calcium). Although the formal oxidation state of the metalin the preferred highly reactive metal species is considered to be zero,it is believed that there is significant charge transfer between themetal and the solubilizing agent. By "in combination" or "incomplexation with" it is meant that the reduction of the soluble metalsalt generates a physical mixture of formally zerovalent soluble metalatoms and the solubilizing agent.

In order to obtain the soluble formally zerovalent metal atoms that area part of the soluble highly reactive metal species, a soluble metalsalt is combined with a solubilized reducing agent in an ethereal,polyethereal or hydrocarbon solvent. Any soluble (as defined above inthe description of a soluble source of electrons) metal salt that can beexposed to a solubilized reducing agent in an ethereal, polyethereal orhydrocarbon solvent to form soluble formally zerovalent metal atoms canbe used in the method of the present invention. These salts includesoluble calcium(II) salts, soluble barium(II) salts, solublestrontium(II) salts and soluble copper(I and/or II) salts. Preferably,soluble highly reactive barium, strontium, or calcium is used in thepresent invention, at least because copper is more difficult tosolubilize. Therefore, soluble barium(II) salts, calcium(II) salts, andstrontium(II) salts are preferred salts to form soluble formallyzerovalent metal atoms.

The counterion of the soluble metal salt can be any of a variety ofanions that does not contain an acidic proton. For example, the anioncan be a sulfate, nitrate, nitrite, cyanide, or halide. Preferably, theanion is a cyanide or a halide. More preferably, the anion is F, Cl Br,or I. Most preferably the anion of the soluble metal salt is Br or I.

Generally, the solubilized reducing agent that is combined with thesoluble metal salt to form formally zerovalent soluble metal atoms canbe any solubilized reducing agent that is capable of reducing solublemetal salts in an ethereal, polyethereal, or hydrocarbon solvent. Anyreducing agent having a reduction potential of -1.5 volts, or morenegative, relative to SCE will satisfy this relation. It is preferred,however, if the reducing agent has a reduction potential of -1.8 voltsor more negative, and most preferred if the reducing agent has areduction potential of about -2.0 volts or more negative. Preferably thereduction of the soluble metal salts takes place in an ethereal orpolyethereal solvent, and more preferably in tetrahydrofuran.

The solubilized reducing agent can be any of the variety of macrocyclicpolyethers, cryptates, polyenes and the like in combination with alkalimetals that are discussed previously as soluble suitable sources ofelectrons useable in the present invention. Examples of suitablesolubilized reducing agents include alkali metal salts of aromaticanions, such salts being, for instance, sodium naphthalenide, lithiumnaphthalenide, sodium anthracenide, lithium anthracenide, sodiumbiphenylide or lithium biphenylide; alkali metal-polyether solvates;alkali metal-crown ether solvates; alkali metal-cryptate solvates, etc.Preferably, the reducing agent is an alkali metal arene salt. Morepreferably, the reducing agent is a combination of an alkali metalcation and an anion of an aromatic electron transfer compound, suchbiphenyl, anthracene, or naphthalene. Most preferably, the reducingagent is preformed. Of the preformed alkali metal arene salts, the mostpreferred is lithium biphenylide.

This variety of macrocyclic polyethers, cryptates, polyenes and the likein combination with an alkali metal (e.g., an alkali metal arene salt)can be used directly as the soluble source of electrons, or they can beused as the solubilized reducing agent to form the soluble highlyreactive metal species, which act as the soluble source of electrons.Solubilized reducing agents can be combined with a soluble metal salt toform a soluble highly reactive species (i.e., soluble formallyzerovalent metal atoms in combination with a solubilizing agent).

The solubilizing agent that is in combination with the formallyzerovalent metal atoms can be any of the variety of macrocyclicpolyethers, cryptates, or polyenes, and the like discussed previouslywith respect to the solubilized reducing agent. The solubilizing agentis obtained from the solubilized reducing agent and is preferablycapable of interacting with the formally zerovalent metal atoms in sucha manner that a less reactive finely divided powder does not precipitateout of solution to any significant extent. By this it is meant that thesoluble formally zerovalent metal atoms are preferably substantiallycompletely soluble in an ethereal, polyethereal, or hydrocarbon solventwith only about 20% or less of the soluble metal atoms in a solid state,i.e., a state without any significant interaction with the solubilizingagent.

Preferably, the solubilizing agent, as provided by the solubilizedreducing agent to be in combination with the formally zerovalent metalatoms, is a polyene. More preferably, the solubilizing agent contains anaromatic polyene, i.e., an arene or polyarylene, such as an aromaticelectron-transfer compound. Thus, in a preferred embodiment, the highlyreactive soluble metal species is composed of formally zerovalentsoluble metal atoms in combination or in complexation with a polyene inan ethereal or polyethereal solvent.

In accord with the present invention, the soluble highly reactive metalspecies, such as calcium, barium or strontium, can be in combinationwith an alkali metal salt wherein the anion does not contain an acidicproton. Because the soluble highly reactive metal species is preferablyutilized within a short period of time after its preparation, it can bein complexation with the alkali metal salt produced from the cation ofthe aromatic reducing agent and the anion of the soluble metal startingmaterial (i.e., soluble metal salt). The alkali metal of the salt can beLi, Na, K, Rb, or Cs. Preferably it is Li, Na, or K, and most preferablyit is Li or Na. The anion can be, but is not limited to, a nitrate,nitrite, sulfate, cyanide, and/or halide. Preferably, the anion is ahalide or cyanide. Generally, this alkali metal salt is not believed toeffect the reactivity of the soluble highly reactive metal species;however, it may facilitate the reactivity of the organic compounds.

In the most specific and preferred embodiment of the soluble highlyreactive metal species, as used as a soluble source of electrons inaccord with the present invention, the metal species is composed offormally zerovalent soluble metal atoms in combination with or complexedwith, biphenyl and a lithium halide in tetrahydrofuran.

Production of the soluble highly reactive metal species is conductedunder conditions designed to prevent its reoxidation and substantialprecipitation as a metal powder. Generally, these conditions include useof ethereal, polyethereal, or hydrocarbon solvents and the exclusion ofoxygen. Also, the conditions are controlled so as to promote theexistence of the metal atoms as small soluble clusters and to avoidtheir agglomeration into larger configurations that could precipitateout of solution. Larger clusters of metal atoms generally means lowersolubility and lower reactivity.

Typically, these conditions include temperatures of about 100° C. orless, an inert atmosphere, e.g., an argon, nitrogen or heliumatmosphere, a reaction time of about one hour, and an ether or polyethersolvent such as diethyl ether, dimethyl ether, tetrahydrofuran and thelike, or a hydrocarbon solvent. By "inert" atmosphere it is meant thatthe atmosphere is not contributing atoms or molecules that areparticipating in the formation of the soluble source of electrons or inthe polymerization process.

Typically, the molar ratio of the solubilized reducing agent to themetal(II) salt, such as a Ca(II) salt, a Ba(II) salt, or a Sr(II) salt,is about 2:1 for a molar equivalent amount; however, the salts can be inexcess. Preferably, the salt is present in an amount of about 1.1-2.0molar equivalents, and more preferably in an amount of about 1.5-2.0molar equivalents, per mole equivalent of reducing agent. Excess salt isused to ensure there is little or no reducing agent present to interferewith subsequent reactions.

In sum, the polymers in accord with the present invention are made bycombining a source of electrons that is soluble in an ethereal,polyethereal, or hydrocarbon solvent with an organic monomer orco-monomer as described herein. Most preferably, the soluble source ofelectrons is lithium biphenylide or lithium naphthalenide.Alternatively, the soluble source of electrons can be a soluble highlyreactive metal species, such as a calcium, barium, or strontium species.

There are at least two methods for preparing the soluble formallyzerovalent highly reactive metal species suitable as a soluble source ofelectrons in accord with the present invention. One method involves aone-step reduction in an ethereal, polyethereal or hydrocarbon solventof a soluble metal salt, such as a Ca(II), Ba(II) or Sr(II) salt.Specifically, this method includes the reduction of a soluble metal saltin the presence of an alkali metal, such as lithium, sodium orpotassium, and an equal molar amount of an electron transfer compound,such as the aromatic electron transfer compound naphthalene or biphenyl.The alkali metal is present in a molar equivalent amount, i.e., in arange of about 1.8-2.2 moles alkali metal per mole of the soluble metalsalt being reduced. It is desirable, however, to use a slight excess ofthe metal salt relative to the alkali metal, to decrease the chance thatthe reducing agent could interfere with the subsequent use of the highlyreactive metal species.

The reduction is typically complete in about 10 hours, and preferably inabout five hours, with vigorous stirring of the mixture. For certainembodiments, the reaction is observed to be "complete" when the greencolor, which is evidence of an alkali metal/aromatic electron transfercomplex, disappears. For other embodiments, the reaction is observed tobe "complete" when the green color appears, and remains. For still otherembodiments, completion of the reduction reaction is evidenced by thedisappearance of lithium and/or lack of formation of the bright greenlithium naphthalenide anion. Stirring may be necessary during thisreaction to prevent the reduced metal from coating unused alkali metaland stopping the reaction.

In this one-step preparation method, the solubilized metal salt, isgenerally always in excess in the reaction flask, relative to the amountof the alkali metal/electron transfer complex present. Herein,"solubilized" salt means the portion of the metal salt that has goneinto solution. For soluble metal salts, this is not necessarily the mostpreferred method of reduction because the surface of the lithium metalcan be coated with metal atoms, which slows down the reduction.

A second method for the preparation of a reactive soluble metal speciesinvolves a two-step reduction of a metal salt in an ethereal,polyethereal or hydrocarbon solvent using a preformed reducing agent. By"preformed" it is meant that for each mole of the alkali metal, about1-1.2 moles of an electron transfer compound are allowed to reactsubstantially completely, i.e., until substantially all the alkali metalis consumed, before contacting any soluble metal salts. The formation ofthe preformed reducing agent preferably takes place in an ethereal,polyethereal, or hydrocarbon solvent, and generally is substantiallycomplete in less than about eight hours, preferably in less than abouttwo hours.

An approximate molar equivalent amount of the metal salt in a solvent,e.g., CaCl₂ in THF, is then slowly (over a period of about 5 to 15minutes) transferred into the solution of the preformed reducing agent,e.g., lithium naphthalenide in THF. Alternatively, the preformedreducing agent can be added to the metal salt.

The reduction of the metal salt in the second step of this two stepmethod using a preformed reducing agent is typically carried out in lessthan about eight hours, preferably in less than about two hours, andmore preferably in less than about one hour. Preferably, the totalreaction time for both steps is less than about eight hours. Thistwo-step method is advantageous for soluble metal salts, when comparedto the previously discussed method, at least because it involves ashorter reaction time and it decreases, if not eliminates, the problemof the resultant reduced metal coating the alkali metal. Generally thismethod forms highly reactive soluble metals of approximately the samereactivity as does the previously discussed method.

The alkali metal complex reducing agents, e.g., lithium naphthalenide,can also be generated by electrochemical reduction of an electrontransfer compound, e.g., naphthalene, using an alkali metal salt, e.g.,a lithium halide, as the electrolyte. That is, an alkali metal complexreducing agent can be formed electrochemically. This can be carried outin an electrochemical cell containing an ethereal or polyetherealsolvent using an electrode of palladium, platinum, carbon, or gold.Useful electrodes can be in any of a variety of forms. They can besolid, porous, or in the form of a slurry. The electrochemical route isadvantageous and preferred at least because it avoids the use of alkalimetals, which can be quite dangerous.

As a representative example of this procedure, naphthalene can bereduced in an inert atmosphere in the presence of a lithium salt, as theelectrolyte, in THF. The electrode can be a large surface area electrodeto facilitate the reduction. Once the lithium naphthalenide is formed,it can be transferred to the metal salt, or the metal salt can betransferred to it, for formation of the soluble zerovalent highlyreactive metal species.

Once formed the soluble zerovalent highly reactive metal can be isolatedand washed to remove any unreacted starting materials, side products, orexcess reducing agent, if so desired. It is generally stable and can bestored for several years at temperatures ranging from 0° C. to 30° C. Itcan be stored in a dry state, in mineral oil as a paste, in an etherealor hydrocarbon solvent as a suspension, or in a paraffin wax matrix. Itis desirable, however, for the zerovalent highly reactive metal to bestored under an inert atmosphere, such as argon, helium or nitrogen.

Carbyne Monomers

Polymers containing carbyne groups can be made from a wide variety ofarylcarbyne monomers, arylcarbyne co-monomers, alkylcarbyne monomers,alkylcarbyne co-monomers, arylalkylcarbyne monomers, arylalkylcarbyneco-monomers, arylcarbyne-alkylcarbyne co-monomers,arylcarbyne-arylalkylcarbyne co-monomers, andalkylcarbyne-arylalkylcarbyne co-monomers. When the soluble source ofelectrons is combined with one of these types of monomers or co-monomersin an ethereal, polyethereal, or hydrocarbon solvent, polycarbynes areformed.

A variety of aryl, alkyl and/or arylalkyl carbyne-containing monomersand co-monomers can be polymerized in accord to the present invention.For example, any arylcarbyne monomers and any alkylcarbyne monomers,such as alkylmonocarbyne monomers, arylbiscarbyne monomers,alkylbiscarbyne monomers, arylbiscarbyne monomers, alkyltriscarbynemonomers and aryltriscarbyne monomers, and mixtures thereof can bepolymerized in accord with the present invention. Specific examplesinclude: α,α,α-trichlorotoluene, 1,1,1-trichloropentane,1,1,1-tribromopropane, 1,1,1,5,5,5-hexachloropentane, and2-trichloromethylnaphthalene.

In addition, these monomers can be combined into co-monomers andpolymerized. Two or more types of arylcarbyne molecules can be combinedto form an arylcarbyne co-monomer, two or more types of alkylcarbynemolecules can be combined to form an alkylcarbyne co-monomer and two ormore types of arylalkylcarbyne molecules can be combined to form anarylalkylcarbyne co-monomer. In addition, one or more types ofalkylcarbyne molecules can be combined with one or more types ofarylcarbyne molecules to form an arylcarbyne-alkylcarbyne comonomer. Forexample, arylmonocarbyne-arylbiscarbyne co-monomers,alkylmonocarbyne-alkylbiscarbyne co-monomers,arylmonocarbyne-alkylmonocarbyne co-monomers,arylmonocarbyne-alkylbiscarbyne co-monomers,arylbiscarbynealkyl-biscarbyne co-monomers, alkylmonocarbyne co-monomers(i.e., two or more different types of alkyl containing molecules can beco-monomers), arylmonocarbyne co-monomers (i.e., two or more differenttypes of aryl containing molecules can be co-monomers), and any othermixture or combination variations of alkylcarbyne, arylcarbyne and/orarylalkylcarbyne co-monomers can all be polymerized to form polycarbynepolymers in accord with the present invention. The polycarbyne polymersformed from co-monomers can be block and/or random polymers. As usedherein, the term "block" refers to a polymer in which molecules of thesame type are grouped together in particular sections of the polymerchain. As used herein, the term "random" refers to a polymer in whichmolecules of the same type may or may not be grouped together in aparticular part of the chain.

The carbyne-containing monomers and/or co-monomers can also containnon-carbyne-containing functional groups or inorganic atoms or groups.Any such group that does not become involved in or interfere with thepolymerization in an ethereal, polyethereal or hydrocarbon solvent, canbe contained in the carbyne-containing monomer or co-monomer of thepresent invention. For example, nitrile and/or ether groups can beattached to an aryl group and/or alkyl group in an arylcarbyne monomeror co-monomer, alkylcarbyne monomer or co-monomer, arylalkylcarbyne orarylcarbyne-alkylcarbyne co-monomer. Therefore, the resulting polymercan contain carbyne groups and other functional groups. Other groups,such as those containing nitrogen, sulfur, phosphorus, oxygen, andsilicon may also be included in the carbyne containing monomer orco-monomer.

The number of carbyne groups and other functional groups contained inthe monomer or co-monomer, and thus, the resulting polymer, can varywith the type of characteristics and/or properties required by thesituation in which the polymer is to be used. The molecule(s) selectedto be included in the monomer or co-monomer will dictate what functionalgroups will be included in the polymer, the number and location of thecarbyne groups bonded to the aryl and/or alkyl groups in the polymer,and many of the polymer's physical properties.

In accord with the present invention the carbyne group(s) can be bondedto an alkyl group contained in a monomer or co-monomer or to anyposition on an aryl group in a monomer or co-monomer. For branched orlong chain alkyl groups, the carbyne is bonded to a terminal carbon,e.g., of a methylene group. Monomers and co-monomers containing one ormore carbyne groups can be polymerized using the methods of the presentinvention. Monomers and co-monomers containing at least two carbon atomsare useable for the present invention. However, monomers and/orco-monomers with at least three carbon atoms and not more than 200carbon atoms are preferred. Monomers and/or co-monomers that have atleast three and not more than 100 carbon atoms are more preferred.

As the variety of molecular structures included in the monomers and/orco-monomers increases, the resulting polycarbyne polymers can havehigher molecular weights, and as the number of different types ofmolecules included in the monomers or co-monomers increases, thepolymers become more soluble. For example, a polycarbyne formed from anarylmonocarbyne-arylbiscarbyne co-monomer typically will have a highermolecular weight and be more soluble in an ethereal, polyethereal orhydrocarbon solvent than a polycarbyne formed from an arylmonocarbynemonomer. In addition, a polycarbyne formed from anarylmonocarbyne-alkylmonocarbyne co-monomer will typically have a highermolecular weight and be more soluble than a polycarbyne formed from anarylmonocarbyne-arylbiscarbyne co-monomer because the latter carbyneco-monomer will be less soluble in an ethereal, polyethereal orhydrocarbon solvent, and thus, will not form chains with a molecularweight as high as a more soluble monomer or co-monomer.

Co-monomers could be utilized in applications requiring higher molecularweight, more soluble, and more amorphous polymers, such as thoseapplications in which films or fibers are formed. For example,arylcarbyne and/or alkylcarbyne co-monomers could be formed into sheetsand treated, preferably pyrolized to make a synthetic diamond materialor formed into fibers to make ropes or protective clothing. Applicationsrequiring harder, stronger, and more crystallized polymers would use anarylcarbyne or alkylcarbyne monomer. For example, arylcarbyne oralkylcarbyne monomers would form polymers that could replace metals.

During polymerization of an alkyl and/or aryl carbyne monomer orco-monomer, the three leaving groups forming the carbyne group with acarbon atom are replaced either directly or indirectly by carbon.Leaving groups should be ions that can be replaced by carbon atoms.Preferably, the leaving groups are easily replaced by carbon atoms in anethereal, polyethereal, or hydrocarbon solvent.

Some examples of leaving groups that could be included in the carbynegroup in accord with the present invention are as follows: a halide, arosylate, a cyanide, an ammonium salt, a phosphonium salt, a triflate, anitrate, a sulfate, and/or a nitrile. Preferably, the leaving groupsincluded in the carbyne group are halides, and most preferably,chlorides.

These three leaving groups are attached to a carbon atom to form acarbyne group, and the carbyne group can be attached to a wide varietyof aryl and alkyl monomer and/or co-monomers, which can then bepolymerized to form polycarbyne polymers. Preferably, the carbyne groupis attached to an aryl compound that polymerizes into apoly(arylcarbyne) when combined with the soluble source of electrons.The aryl monomers can have one or more aromatic rings, and the carbynegroups can be attached to any position on the aryl moiety. For example,carbyne groups can be attached to the para, ortho or meta positions ofone or more phenyl groups. Some examples of aryl monomers that can beused in the present invention include, but are not limited toα,α,α-trihalotoluene, 1- or 2-trihalomethylnaphthalene,1,4-bis(trihalomethyl)-benzene, 2-trihalomethylanthracene, and the like.Preferably, a trihalotoluene, such as α,α,α-trichlorotoluene or1,4-bis(trichloromethyl)-benzene is used in the present invention.

In accord with the present invention, the aryl group in the monomercould be replaced with an alkyl group. In this embodiment, the solublesource of electrons reacts with a carbyne-containing alkyl monomer orco-monomer to form a poly(alkylcarbyne) polymer. Some examples ofcarbyne-containing alkyl monomers that can be used in the presentinvention include, but are not limited to: 1,1,1-trihalopropane,1,1,1,3,3,3-hexahalopropane, 1,1,1-trihalobutane,1,1,1,5,5,5-hexahalopentane or 1,1,1-trihalopentane and the like.

In another embodiment, aryl and/or alkyl carbyne-containing compoundscan be combined to form a co-monomer that can be polymerized in accordwith the present invention. Different alkyl or aryl- or alkylaryl-carbyne-containing molecules can be combined to form a co-monomer. Forexample, a 1,1,1-trihalopentane can be combined with a1,1,1,-trihalobutane to form an alkyl co-monomer, which polymerizes intoa poly(alkylcarbyne), or a 2-trihaloanthracene can be combined with anα, α,α-trihalotoluene to form a poly(arylcarbyne).

Moreover, an arylcarbyne-containing compound and anarylbiscarbyne-containing compound can be combined in virtually anyproportional amounts to form an arylbiscarbyne-arylmonocarbyneco-monomer, for example. In addition, an alkyl carbyne-containingcompound can be combined with an alkylbiscarbyne-containing compound toform an alkylbiscarbyne-alkylmonocarbyne co-monomer. These co-monomerpolymerize into soluble poly(arylcarbyne) and poly(alkylcarbyne)compounds that can exhibit higher molecular weights and higher yields(i.e., over 80%). The films made of these novel polymers can alsoexhibit less cracking and more adhesion than films of polymers formedfrom a monomer containing one type of arylcarbyne or alkylcarbynemolecule. Although the mono alkylcarbyne and bisalkylcarbyne and themonoarylcarbyne and bisarylcarbyne co-monomers can be combined in anyproportion to form an alkylcarbyne co-monomer and/or an arylcarbyneco-monomer in accord with the present invention, a mono and bisco-monomer with 40% or less of the bis-molecule is preferred.

A monomer, in accord with the present invention, may contain any numberof different types of molecules. Furthermore, several differentalkylcarbyne-containing molecules may be combined to form a co-monomer,several different arylcarbyne-containing molecules, for example, .may becombined to form a co-monomer, or several different aryl and alkylcarbyne-containing molecules may be combined to form a co-monomer. Anymonomer useable in the present invention is available commercially orcan be prepared by a specialty chemical company, such as AldrichChemical Co. in Milwaukee, Wis. The carbyne molecules that form aco-monomer can be combined in any proportional amount in an ethereal,polyethereal or hydrocarbon solvent to form a co-monomer. The number ofand amount of the different molecules included in the co-monomer will bedependent upon the application in which the resulting polycarbyne willbe used. The amount of each different type of molecule in a co-monomerto be polymerized into a synthetic diamond material, for example, canvary, but preferably will contain no more than 40 mol-% of one type ofmolecule.

The source of soluble electrons and the organic monomers and co-monomerare combined under conditions to preserve the reactivity of the solublesource of electrons. These conditions include atmospheric pressure,relatively low temperatures (i.e., less than about 100° C.), and anenvironment containing an inert gas. Preferably, the source of solubleelectrons and the organic reactants are combined in an ethereal,polyethereal, or hydrocarbon solvent under an inert gas, such as argon,nitrogen and/or helium, at temperatures well below 100° C. Morepreferably, the source of soluble electrons and the aryl and/or alkylreactants are combined in an ethereal or polyethereal solvent underargon at temperatures below 0° C. After combining the reactants at lowtemperatures, the mixture is then warmed to room temperature (i.e., 25°C. to 30° C.) and refluxed at a higher temperature. The reaction mixtureis then cooled to room temperature and water is added slowly. Theorganic and aqueous layers are separated by any means well-known in theart, and the organic layer is filtered and concentrated under vacuum.Addition of a solvent, such as methanol to the organic layer, gives aprecipitate, which should be collected by filtration and purified byreprecipitation with a solvent such as ethanol, from the ethereal,polyethereal, or hydrocarbon solvent. The product should then be driedunder vacuum.

Polycarbyne Polymers

Generally, the resulting polycarbynes are novel. These polycarbynes havea tetrahedral three dimensional network, which is formed duringpolymerization and is much like the three dimensional network of naturaldiamond. This tetrahedral three dimensional network differentiatespolycarbynes from other two dimensional linear or branched polymers thathave the same formulas as polycarbynes. These polycarbynes are,typically, solid strong polymers that withstand extreme conditions andcan be used to form a variety of types of materials. For example, thesepolymers can be resolubilized to form films and then pyrolized, orotherwise appropriately treated, to make synthetic diamond materials.These polycarbynes can be resolubilized to form fibers and filaments tomake protective clothing. Many of these novel polyarylcarbynes and/orpolyalkylcarbynes and the like can be used to replace metal and otherhard solid materials. Some examples of these resulting polymers include:poly(phenylcarbyne), poly(phenyldicarbyne), poly(methyldicarbyne),poly(propylcarbyne) and the like.

The present invention, typically, provides reasonably high yields ofthese polycarbynes. Preferably, the yields in accord with the presentinvention are at least about 30%, more preferably at least about 40%,and most preferably at least about 60%.

The molecular weights of these polymers can vary according to theapplication for which they are used. Preferably, the polymers have anaverage molecular weight of at least about 5,000. More preferably, thepolymers have an average molecular weight of at least about 10,000 andnot greater than about 200,000. The number of monomer units that areincluded in the polymer can also vary. The length of the polymer istypically determined by the type of polymeric material to be formed, andthe application in which the polymeric material will be used. There areat least two monomer units in the polymer. Preferably, the number ofmonomer units included in the polymer is at least two and not greaterthan about 500,000. More preferably, there at least about 10 and notmore than about 100,000 monomer units included in the polymer.

Overall, the polycarbyne polymer has a three-dimensional tetrahedralstructure much like natural diamond. During polymerization, the leavinggroups, attached to the carbon atom that is included in the carbynegroup, are replaced by the carbon atoms included in the carbyne groupsof other monomer or co-monomer molecules, and the number ofcarbon-carbon bonds increases. Due to the large number of carbon-carbonbonds, the resulting polymer can withstand a variety of extremeconditions.

The following are examples of general configurations for polycarbynepolymers in accord with the present invention. The first formula (1)represents a polycarbyne formed from a monocarbyne monomer. ##STR1## The"R" represents the aryl, alkyl or arylalkyl group containing at leastone carbon and not more than 100 carbon atoms that is bonded to thecarbyne group in the monocarbyne monomer. In this particularrepresentation R is the same throughout the polymer. Preferably, "R"contains at least one and not more than 50 carbon atoms, and morepreferably not more than 25 carbon atoms. If R is an arly group, itpreferably has at least seven carbon atoms and more preferably at leastten carbon atoms. The "p" represents the number of monomer unitscontained in the polycarbyne polymer and is at least two. Preferably,"p" is at least three and not greater than about 500,000. Morepreferably, "p" is at least three and not greater than about 100,000.

The second formula (2) represents a polycarbyne formed from amonocarbyne co-monomer containing two different types of monocarbynemolecules. ##STR2## The "R¹ " represents the aryl, alkyl or arylalkylgroup containing at least one carbon and not more than 100 carbon atomsthat is bonded to the carbyne group in one of the monomer unitscontained in the co-monomer. The "R² " represents the aryl, alkyl orarylalkyl group containing at least one carbon and not more than 100carbon atoms that is bonded to the carbyne group in another monomer unitcontained in the co-monomer. The aryl, alkyl or arylalkyl group of R¹ isdifferent from the aryl, alkyl or arylalkyl group of "R² ". Preferably,R¹ and R² each contain at least two carbon atoms and not more than 50carbon atoms, and most preferably each does not contain more than 25carbon atoms. The "p" represents the number of R¹ monocarbyne moleculescontained in the polycarbyne and is at least one. Preferably, p is atleast one and less than about 500,000. More preferably, p is at leastone and less than about 100,000. The "n" represents the number of R²monocarbyne molecules contained in the polycarbyne, and n is at leastone. Preferably, n is at least one and less than about 500,000. Morepreferably, n is at least one and less than about 100,000. Mostpreferably, the sum of p and n is not greater than about 100,000. Thedotted line representing the bond between the carbyne groups containedin each type of molecule indicates that the molecules can be in a randomor block sequence in the polymer chain. Additional formulas can bewritten for three or more monocarbyne molecules that each containdifferent "R" groups. In general, the polycarbynes resulting from all ofthe varieties of monocarbyne monomers and monocarbyne co-monomersuseable in the present invention are represented by formula (3).##STR3## As shown by formulas (1) and (2), R can be the same ordifferent, and preferably, each different R contains at least one andnot more than 100 carbon atoms. More preferably, each different Rcontains at least two and not more than 50 carbon atoms. Mostpreferably, each different R contains at least two and not more than 25carbon atoms. If R is the same in each monomer unit and is an arylgroup, it preferably has at least seven carbon atoms and more preferablyat least ten carbon atoms. The "p" in formula (3) is at least two andrepresents the number of monomer units in the polycarbyne. Preferably, pis at least two and not greater than about 500,000. More preferably, pis at least two and not greater than about 100,000. A polycarbyne formedfrom a monocarbyne co-monomer may be in a random or block sequence.

The same type of general formula can represent a polydicarbyne, which isformed from a biscarbyne monomer or a biscarbyne co-monomer. Formula (4)represents the general formula for a polydicarbyne. As stated above, Rcan be the same or different, from monomer unit to monomer unit, andwhen R is different, a random or block polymer can be formed. ##STR4##Moreover, the same type of formula can represent a polycarbyne formed bycombining at least one monocarbyne molecule and one biscarbyne molecule.Formula (5) represents a polycarbyne formed from amonocarbyne-biscarbyne co-monomer. ##STR5## In formula (5), aspreviously stated, R can be the same or different, and when R isdifferent, a random or block polymer can be formed. The "n" representsthe number of monocarbyne molecules in the polymer, and the "p"represents the number of biscarbyne molecules in the polymer. The "n" isat least one. The "p" is at least one. The sum of n and p is the totalnumber of monomer units in the polymer. The sum of n and p is at leasttwo and preferably, at least two and not greater than about 500,000.Most preferably, the sum of n and p is at least two and not greater than100,000. Polycarbynes can also be formed from monomers and/orco-monomers containing molecules that have more than two carbyne groups.As shown by formula (5), molecules containing more than one carbynegroup can combine with molecules containing one or more carbyne groupsto form a co-monomer. Formula (6) represents the three dimensionaltetrahedral network of any polycarbyne in accord with the presentinvention. ##STR6## The "i" represents the number of carbyne groups in amonomer unit and can vary from monomer unit to monomer unit. There is atleast one carbyne group in each monomer unit. R as stated above, can bethe same or different, and when different, a random or block polymer canbe formed. The "p" represents the number of monomer units in the polymerand is at least two. Preferably, p is at least two and not greater thanabout 500,000. More preferably, p is at least two and not greater thanabout 100,000.

As required, detailed embodiments of the present invention are disclosedherein. However, it is to be understood that the disclosed embodimentsare merely exemplary of the present invention which may be embodied invarious systems. Therefore, specific details disclosed herein are not tobe interpreted as limiting, but rather as a basis for the claims and asa representative basis for teaching one skilled in the art to variouslypractice the present invention.

EXPERIMENTAL EXAMPLES

¹ H NMR (CDCl₃) spectra were obtained using an Omega-500 (500 MHz) or anOmega-300 (300 MHz) NMR spectrometer. All chemical shifts are reportedin parts per million (δ) downfield from internal tetramethylsilane.Fully decoupled ¹³ C NMR spectra and were obtained from an Omega-500(500 MHz) or an Omega-300 (300 MHz) NMR spectrometer. The center peak ofCDCl₃ (77.0 ppm) was used as the internal reference. IR spectra weretaken on an Analect RFX-65 Fourier Transform Infrared (FTIR)spectrometer. The spectra were taken with neat polymer film cast fromCHCl₃ solution on NaCl disks. Fluorescence spectra were taken on aShimadzu RF-540 spectrofluorophotometer with a polymer solution ofcyclohexane (excitation wavelength=300 nm). UV-vis spectra were taken ona Shimadzu UV 160 U recording spectrophotometer with polymer solution incyclohexane. Low-temperature reactions were performed utilizing a NeslabEndocal™ ULT-80 refrigerated circulating bath or utilizing dryice/acetone baths. All manipulations were carried out on a dual manifoldvacuum/argon system. The Linde# prepurified grade argon was furtherpurified by passing it through a 150° C. catalyst column (BASF™ R3-11),a phosphorous pentoxide column, and a column of granular potassiumhydroxide. Lithium and naphthalene, biphenyl, or anthracene were weighedout and charged into reaction flasks under argon in a Vacuum AtmospheresCompany dry box. Molecular weights were determined on a Waters GPC(relative polystyrene standard) with a Waters Ultrastyragel linearcolumn at room temperature using tetrahydrofuran (THF) as the eluent.Tetrahydrofuran was freshly distilled under argon from sodium-potassiumalloy. Pentane was dried over a sodium-potassium alloy. Reagents werepurchased from Cerac, Inc. or Aldrich Chemical Co., both of Milwaukee,Wis.

EXAMPLE 1 Preparation of Poly(phenylcarbyne) Using Highly ReactiveCalcium

Lithium (0.06 mol) and biphenyl (0.066 mol) in a 100 ml flask werestirred in freshly distilled tetrahydrofuran (THF) (40 ml) at roomtemperature under argon until the lithium was completely consumed(approx. 2 hours). To a well-suspended solution of CaI₂ (0.03 mol) inTHF (40 ml) in a 250 ml flask, the preformed lithium biphenylide wastransferred via cannula at room temperature (i.e., about 25° C. to about30° C). The solution of highly reactive calcium was stirred for one hourat room temperature. The highly reactive calcium is dark-green in colorand is essentially homogeneous in THF. A solution ofα,α,α-trichlorotoluene (0.019 mol) in 10 ml dry pentane was then addedvia a cannula at -78° C. The reaction mixture was then warmed to roomtemperature and refluxed for four hours at 67° C. The reaction mixturewas then cooled to room temperature, and 100 ml of water were addedslowly. The organic layer was then separated from the aqueous layer. Theorganic layer was faltered and concentrated in volume to 25 ml undervacuum. Addition of methanol (100 ml) to the organic layer gave a tanprecipitate, which was collected by filtration and purified byreprecipitation with ethanol from a THF solution. The yielded tan powderwas dried at 100° C. under vacuum for 24 hours, giving 0.80 g (46%) ofpoly(phenylcarbyne). ##STR7## The spectral analysis (FTIR, ¹ H & ¹³ CNMR, UV, Fluorescence) proved the polymer obtained using thismethodology was almost exactly the same as the poly(phenylcarbyne)reported by Visscher et al. in Science., 260, 1496-1499 (1993). Thepoly(phenylcarbyne) is a random three-dimensional network. Infraredspectra showed only monosubstituted phenyl groups present (strongabsorbance at 698 cm⁻¹ (δmono₁) and 756 cm¹ (δmono₂) for twoout-of-plane vibrations of monosubstituted benzene ring). No absorbanceof di- and tri-substituted benzene rings was found. No absorbance ofaliphatic C═C was found. The ¹ H NMR spectrum displayed a dominantaromatic proton resonance at 7.3 parts per million (ppm). The terminalproton of the polymer network caused the very weak resonance around 3.5ppm. The ¹³ C NMR spectrum exhibited three resonances, one center at 140ppm is attributed to the ipso-carbon of phenyl ting, and an intensiveresonance at 128 ppm is caused by the other five carbons of phenyl ring,a very broad resonance center at 50 ppm is caused by the quaternarycarbon of poly(phenylcarbyne).

As shown in FIG. 1, the UV-vis electronic spectrum exhibited an intensebroad absorption which started at a wavelength λ≦200 nm and decreased to460 nm. Corresponding to the electronic absorbance, an intensive, broadfluorescence peak with λ_(max) at 460 nm was found in the fluorescencespectrum of the polymer. Both UV-vis and fluorescence properties wereconsistent with the poly(phenylcarbyne) structure. The elementalanalysis of the polymer compared well with the empirical formula (C₆ H₅C)_(n) of poly(phenylcarbyne).

EXAMPLE 2 Preparation of Poly(phenylcarbyne) Using Highly ReactiveStrontium

For Example 2, the same procedure as disclosed in Example 1 wasfollowed. However, instead of using CaI₂ and reducing calcium, SrBr2 wasused and strontium was reduced. This method produced a 42% yield ofpoly(phenylcarbyne). The spectral data for the resulting compound wasalso the same as disclosed in Example 1.

EXAMPLE 3 Preparation of Poly(phenylcarbyne) Using Highly ReactiveBarium

For Example 3, the same procedure as disclosed in Example 1 wasfollowed. However, BaI₂ was used instead of CaI₂, and therefore bariuminstead of calcium was reduced. This method produced a 42% yield ofpoly(phenylcarbyne). The resulting compound had spectral data analogousto that disclosed in Example 1.

EXAMPLE 4 Preparation of Poly(phenylcarbyne) Using Lithium and Biphenyl

Lithium (0.06 mol) and biphenyl (0.066 mol) in 100 ml flask were stirredin freshly distilled THF (40 ml) at room temperature under argon untilthe lithium was completely consumed (approx. 2 hours). A solution ofα,α,α-trichlorotoluene (0.019 mol) in 10 ml dry THF was the added viacannula at -78° C. The reaction mixture was then warmed to roomtemperature and refluxed for 4 hours at 67° C. The reaction mixture wasthen cooled to room temperature and 100 ml of water were added slowly.The organic layer was then separated from the aqueous layer. The organiclayer was filtered and concentrated in volume to 25 ml under vacuum.Addition of methanol (100 ml) to the organic layer gave a tanprecipitate, which was collected by filtration and purified byreprecipitation with ethanol from a THF solution. This precipitate wasthen dried under vacuum at 100° C. for 24 hours, giving 1.03 g (61%) ofpoly(phenylcarbyne).

¹ H NMR (500 MHz, CDCl₃): δ=7.4 ppm (br, C₆ H₅). ¹³ C NMR (500 MHz,CDCl₁₃): δ=140, 128 (br, C₆ H₅ s), and 50 ppm (br, C₆ H₅ C). Infrared(film cast from CHCl₃ solution onto NaCl disc): 3053(s), 3022(s),2920(s), 2930(s), 2850(s), 1948(m), 1884(m), 1805(w), 1600(s), 1493(s),1180(m), 1157(m), 1030(m), 914(w), 756(s), 667(w), 696 cm⁻¹ (s). UV-vis(cyclohexane): onset at 460 nm, increased gradually in intensity withdecreasing wavelength to 200 nm. Fluorescence (cyclohexane, excitationwavelength=300 nm): λ_(max) =460 nm.

EXAMPLE 5 Preparation of Poly(phenyldicarbyne) Using Highly ReactiveBarium

Lithium (0.06 mol) and biphenyl (0.066 mol) in a 100 ml flask werestirred in freshly distilled THF (50 ml) at room temperature under argonuntil the lithium was completely consumed (approx. 2 hours). To awell-suspended solution of BaI₂ (0.03 mol) in THF (30 ml) in a 250 mlflask, the preformed lithium biphenylide was transferred via a cannulaat room temperature. The solution of highly reactive barium was stirredfor one hour at room temperature. A solution of1,4-bis(trichloromethyl)-benzene (0.01 mol) in 10 ml dry THF was thenadded at a controlled rate over 30 minutes via cannula at -78° C. Thereaction mixture was then warmed to room temperature and refluxed fortwo hours at 67° C. The reaction mixture was then cooled to roomtemperature and 100 ml water were added slowly, after which the organiclayer was separated from the aqueous layer. The organic layer wasfiltered, and the precipitate was collected and extracted with methanoland hexane, dried under a vacuum at room temperature for 24 hours andresulted in 1.05 g (100%) poly(phenyldicarbyne), which was ayellow-brown insoluble powder. Infrared (KBr pressed pellet): 3053(s),3022(s), 2920(s), 2930(s), 2850(s), 1948(m), 1884(m), 1805(w), 1600(s),1493(s), 1444(s), 1180(m), 1157(m), 1030(m), 914(w), 835(s), 760(w), and698(w) cm⁻¹. The strong Peak for 1,4-disubstituted benzene appeared.##STR8##

EXAMPLE 6 Preparation of Poly(propylcarbyne) Using 1,1,1,-trichloropropane.

Lithium (0.06 mol) and biphenyl (0.066 mol) in a 100 ml flask is stirredin freshly distilled tetrahydrofuran (THF) (40 ml) at room temperatureunder argon until the lithium is completely consumed (approx. 2 hours).To a well-suspended solution of CaI₂ (0.03 mol) in THF (40 ml) in a 250ml flask, the preformed lithium biphenylide is transferred via cannulaat room temperature. The solution of highly reactive calcium is stirredfor one hour at room temperature. The highly reactive calcium isdark-green in color and is essentially homogeneous in THF. A solution of1,1,1-trichloropropane (0.019 mol) in 10 ml dry pentane is then addedvia a cannula at -78° C. The reaction mixture is then warmed to roomtemperature and refluxed for four hours at 67° C. The reaction mixtureis then cooled to room temperature, and 100 ml of water are addedslowly. The organic layer is then separated from the aqueous. Theorganic layer is filtered and concentrated in volume to 25 ml in vacuum.The product is isolated upon the addition of methanol (100 ml) to theorganic layer, collection by filtration and purification byreprecipitation with ethanol from THF solution.

EXAMPLE 7 Preparation of Poly(methyldicarbyne) Using1,1,1,3,3,3-hexachloropropane

Lithium (0.12 mol) and biphenyl (0.132 tool) in a 100 ml flask isstirred in freshly distilled tetrahydrofuran (THF) (80 ml) at roomtemperature under argon until the lithium is completely consumed(approx. 2 hours). To a well-suspended solution of CaI₂ (0.06 mol) inTHF (80 ml) in a 250 ml flask, the preformed lithium biphenylide istransferred via cannula at room temperature. The solution of highlyreactive calcium is stirred for one hour at room temperature. The highlyreactive calcium is dark-green in color and is essentially homogeneousin THF. A solution of 1,1,1,3,3,3-hexachloropropane (0.019 mol) in 10 mldry pentane is then added via a cannula at -78° C. The reaction mixtureis then warmed to room temperature and refluxed for four hours at 67° C.The reaction mixture is then cooled to room temperature, and 100 ml ofwater are added slowly. The organic layer is then separated from theaqueous. The organic layer is filtered and concentrated in volume to 25ml under vacuum. The product is isolated upon the addition of methanol(100 ml) to the organic layer, collection by filtration, purification byreprecipitation with ethanol from THF solution.

EXAMPLE 8 Preparation of a Polycarbyne Using a Monocarbyne-BiscarbyneCo-Monomer

Lithium (0.06 mol) and biphenyl (0.066 mol) in a 100 ml flask werestirred in freshly distilled THF (40 ml) at room temperature under argonuntil the lithium was completely consumed (approx. two hours). To asolution of α,α,α-trichlorotoluene (0.016 mol) and1,4-bis(trichloromethyl)-benzene (0.0016 mol) in 20 ml dry THF in a 250ml flask, the preformed lithium biphenylide was transferred at acontrolled rate over 30 minutes via cannula at -78° C. The reactionmixture was then warmed to room temperature and refluxed for 10 hours at67° C. The reaction mixture was then cooled to room temperature and 100ml of water were added slowly. The organic layer was then separated fromthe aqueous layer. The organic layer was filtered and concentrated involume to 40 ml under a vacuum. When methanol (100 ml) was added to theorganic layer, a brown precipitate formed. The precipitate was collectedby filtration and purified by reprecipitation with ethanol from THFsolution. The precipitate was then dried under a vacuum at 100° C. for24 hours giving 1.20 g (76%) of a poly(phenylcarbyne) tan powder.##STR9##

What is claimed is:
 1. A method for preparation of a polycarbynecomprising: contacting a source of electrons which is soluble in anethereal, polyethereal or hydrocarbon solvent and has a reductionpotential of -0.2 or more negative relative to the standard calomelelectrode with a carbyne containing organic monomer or co-monomer in anethereal, polyethereal or hydrocarbon solvent to form a polycarbyne;wherein said organic monomer contains at least one carbyne group andsaid soluble source of electrons is soluble in an ethereal,polyethereal, or hydrocarbon solvent.
 2. The method of claim 1 whereinthe source of electrons is at least 0.5 wt-% soluble.
 3. The method ofclaim 1 wherein the carbyne containing organic monomer or co-monomercontains one carbyne group.
 4. The method of claim 3 wherein the carbynecontaining organic monomer or co-monomer is an arylcarbyne.
 5. Themethod of claim 3 wherein the carbyne containing organic monomer orco-monomer is an alkylcarbyne.
 6. The method of claim 1 wherein thecarbyne containing organic monomer or co-monomer contains twocarbyne-groups.
 7. The method of claim 6 wherein the carbyne containingorganic monomer or co-monomer is an arylbiscarbyne.
 8. The method ofclaim 7 wherein the carbyne containing organic monomer or co-monomer isa phenylbiscarbyne.
 9. The method of claim 6 wherein the carbynecontaining organic monomer or co-monomer is an alkylbiscarbyne.
 10. Themethod of claim 1 wherein the carbyne containing organic monomer orco-monomer is an arylalkylcarbyne co-monomer.
 11. The method of claim 1wherein the carbyne containing co-monomer comprises a monocarbyne moietyand a biscarbyne moiety.
 12. The method of claim 10 wherein the carbynecontaining co-monomer contains an alkylcarbyne and an arylcarbynecompound.
 13. The method of claim 1 wherein the source of electrons is acomplex of an alkali metal and an electron transfer compound.
 14. Themethod of claim 13 wherein the source of electrons is an alkali metalcomplex of naphthalene, biphenyl, or anthracene.
 15. The method of claim14 wherein the source of electrons is lithium naphthalenide or lithiumbiphenylide.
 16. The method of claim 1 wherein the source of electronsis a highly reactive non-alkali metal species.
 17. The method of claim16 wherein the source of electrons is a highly reactive barium,strontium, copper or calcium species.
 18. A method for preparation of apolycarbyne comprising: (a) contacting in an ethereal, polyethereal, orhydrocarbon solvent a metal salt, soluble in an ethereal, polyetherealor hydrocarbon solvent, with a solubilized reducing agent having areduction potential of -1.5 volts or more negative relative to thestandard calomel electrode, to form a soluble highly reactive metalspecies;(b) contacting the soluble highly reactive metal species with anorganic monomer or co-monomer in an ethereal, polyethereal orhydrocarbon solvent to form a polycarbyne; wherein said organic monomercontains at least one carbyne group and said highly reactive metalspecies is soluble in an ethereal, polyethereal, or hydrocarbon solvent.19. The method of claim 18 wherein the metal salt is a Ca(II) salt,Ba(II) salt, Cu(I) salt, Cu(II) salt, or Sr(II) salt.
 20. The method ofclaim 18 wherein the solubilized reducing agent is an alkali metalcomplex of naphthalene, biphenyl, or anthracene.
 21. The method of claim20 wherein the solubilized reducing agent is lithium naphthalenide orlithium biphenylide.
 22. A method for preparation of apoly(alkylcarbyne) comprising:contacting a source of electrons which issoluble in an ethereal, polyethereal or hydrocarbon solvent and has areduction potential of -0.2 or more negative relative to the standardcalomel electrode with an organic monomer in an ethereal, polyetherealor hydrocarbon solvent to form a poly(alkylcarbyne); wherein the organicmonomer contains at least one carbyne group bonded to an alkyl group.23. A method for preparation of a poly(arylcarbyne)comprising:contacting a source of electrons which is soluble in anethereal, polyethereal or hydrocarbon solvent and has a reductionpotential of -0.2 or more negative relative to the standard calomelelectrode with an organic monomer in an ethereal, polyethereal orhydrocarbon solvent to form a poly(arylcarbyne); wherein the organicmonomer contains at least one carbyne group bonded to an aryl group. 24.The method of claim 23 wherein the organic monomer contains at least onecarbyne group bonded to a phenyl group.
 25. The method of claim 24wherein the organic monomer is α,α,α-trichlorotoluene.
 26. A method forpreparation of polymer fibers comprising:(a) contacting a source ofelectrons which is soluble in an ethereal, polyethereal or hydrocarbonsolvent and has a reduction potential of -0.2 or more negative relativeto the standard calomel electrode with an organic monomer in anethereal, polyethereal or hydrocarbon solvent to form a polycarbyne;wherein the organic monomer or co-monomer contains at least one carbynegroup; and (b) forming fibers from the polycarbyne.
 27. The method ofclaim 26 wherein the organic monomer or co-monomer contains at least onecarbyne group bonded to a phenyl group.
 28. A polycarbyne of thefollowing formula: ##STR10## wherein: (a) said polycarbyne comprises atetrahedral three dimensional network;(b) i=at least one and representsthe number of carbyne groups in a monomer unit; (c) R=a (C₁₀₀) alkylgroup, a (C₇₋₁₀₀) aryl group or a (C₁₋₁₀₀) arylalkyl group; (d) p=atleast two and represents the number of monomer units in the polycarbyne;and (e) each R and each i can be the same or different.
 29. Apolycarbyne of claim 28 wherein i=1 for every monomer unit.
 30. Apolydicarbyne of the following formula: ##STR11## wherein: (a) saidpolycarbyne comprises a tetrahedral three dimensional network andwherein(b) R=a (C₁₋₁₀₀) alkyl group, a (C₆₋₁₀₀) aryl group or a (C₇₋₁₀₀)arylalkyl group; (c) p=at least two and represents the number of monomerunits in the polycarbyne; and (d) R can be the same or different.
 31. Apolycarbyne of the following formula: ##STR12## wherein: (a) saidpolycarbyne comprises a tetrahedral three dimensional network;(b) R=a(C₁₋₁₀₀) alkyl group or a (C₆₋₁₀₀) aryl group or a (C₇₋₁₀₀) arylalkylgroup; (c) p=is at least one; (d) n=is at least one; and (e) R can bethe same or different.
 32. A polymer fiber prepared from a tetrahedralthree dimensional polycarbyne having a formula: ##STR13## wherein i=atleast one and represents the number of carbyne groups in a monomerunit;R=a (C₁₋₁₀₀) alkyl group or a (C₆₋₁₀₀) aryl group or a (C₇₋₁₀₀)arylalkyl group; p=is at least two and represents the number of monomerunits in the polycarbyne; and wherein each R and each i can be the sameor different.
 33. A method for preparation of a poly(phenyldicarbyne)comprising: contacting a source of electrons which is soluble in anethereal, polyethereal or hydrocarbon solvent and has a reductionpotential of -0.2 or more negative relative to the standard calomelelectrode with an organic monomer in an ethereal, polyethereal orhydrocarbon solvent to form a poly(phenyldicarbyne); wherein saidorganic monomer contains two carbyne groups bonded to a phenyl group andwherein said soluble source of electrons is soluble in an ethereal,polyethereal, or hydrocarbon solvent.